Novel class of 3-indazolinone developing agent



United States Patent.

Jersey No Drawing. Filed May 23, 1960, Ser. No. 30,777 21 Claims. (Cl. 96-55) This invention relates to a novel class of photographic developing agents and their use in developer solutions to produce images in exposed light-sensitive silver halide emulsions.

Photographic developing agents of the aromatic amine type such as the aminophenols and the phenylenediamines, and the substituted 3-pyrazolidones useful for producing silver images in exposed light-sensitive silver halide emulsion layers, are old. These developing agents are usually used in alkaline developer solutions containing an alkali sulfite as well as other components depending upon the particular requirements. Frequently, two different developing agents may be used together in such a developer in order to furnish a developer which has the desired amount of activity and which produces a developed image with desirable sensitometric characteristics. By sensitometric characteristics We mean the relationship between the developed image density and the amount of'light exposure given to the light-sensitive emulsion layer. Usually, images with low minimum densities, high maximum densities and uniform density changes (with exposure) between the minimum and maximum densities are desired.

The silver images developed in photographic emulsion layers are fixed by treating the emulsion in an alkali thiosulfate bath by a process well known in the art.

p-Phenylenediamine-type developing agents in which a hydrogen atom of one of the amino groups is replaced with an alkyl group are usually used in developer solutions for developing dye images. During the color development of an exposed light-sensitive silver halide emulsion layer, the oxidized developing agent produced by the silver image development, couples with a color-forming coupler compound that is present to form a dye image. The coupler compound may either be incorporated in the emulsion layer or be dissolved in the developer solution.

Some of the available agents do not have the desired developing activity and developers containing them are thus characterized by low developing rates. Such developers usually do not produce as high a maximum density as is desired in a reasonable time of development. Some developers produce a minimum or fog density that is higher than is desired.

Complex developer solutions containing not only a developing agent but also a color-forming coupler compound must be used to produce a dye image by color development of an exposed light-sensitive silver halide emulsion layer which does not contain an incorporated coupler. Such solutions are not only expensive to prepare but are frequently characterized by having relatively poor stability on keeping.

It is therefore an object of the invention to provide a novel class of photographic developing agents that have good developer activity.

Another object is to provide a novel class of 3-indazolinone developing agents which are useful as the developing agent in an alkaline developer solution containing from 10 to 200 grams per liter of an alkali sulfite for developing silver images in exposed light-sensitive silver halide emulsion layers.

Another object is to provide a novel class of amino-3- indazolinones that are not only useful as developing agents in developer solutions containing from 10 to 200' 3,043,694 Patented July 10, 1962 ice I grams of an alkali sulfite for developing silver images but a class of developing agents which undergo auto-coupling reactions when used in alkaline developing solutions containing from 0 to 10 grams per liter of an alkali sulfite for simultaneous development of silver and dye images in exposed light-sensitive silver halide emulsion layers containing no incorporated coupler.

Another object is to provide an alkaline photographic developer solution which contains from 10 to 200 grams per liter of an alkali sulfite and as the sole developing agent a B-indazolinone for developing silver images in exposed light-sensitive silver halide emulsion layers.

Another object is to provide an alkaline developer which contains from 0 to 10 grams per liter of an alkali sulfite and an amino-B-indazolinone as the sole developing agent, useful for developing a silver and dye image in an exposed light-sensitive silver halide emulsion layer not containing an incorporated color-forming coupler.

A still further object is to provide a simplified developer solution for producing dye images useful in color photography.

A still further object is to provide developer solutions containing indazolinone developing agent along with a second silver halide developing agent such as p-aminophenol, ascorbic acid, a hydroquinone or a 3-pyrazolidone.

Still further objects 'Will appear from the following specification and claims.

We have discovered that the above objects can be accomplished by the use of 3-indazolinone as the developing agent in alkaline developer solutions of our invention.

The 3-indazolinones useful as developing agents in our developer are represented by the following formula:

C-N-NH (II) R4 in which R R R and R are hydrogen atoms, alkyl groups having from one to six carbon atoms which may be either straight-chain or branched-chain groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, etc., substituted alkyl groups having from one to six carbon atoms in which the alkyl groups may be either straight or branched-chain and in which they may be substituted with any of the commonly used substituents such as halogen atoms, hydroxyl groups, etc., alkoxy groups having from one to six carbon atoms such as methoxy, ethoxy, n-propoxy, ispropoxy, butoxy, isobutoxy, tertiarybutoxy, amyloxy, hexoxy, etc., aryl groups such as phenyl, alkphenyl in which the alkyl group has from one to six carbon atomsas defined above, e.g., Z-methylphenyl, 3-ethylphenyl, 4-propylphenyl, 2-isopropylphenyl, 3-butylphenyl, 4-amylphenyl, 4-hexylphenyl, etc., alkoxyphenyl in which the alkoxy group has I from one to six carbon atoms as defined above such as 2-methoxyphenyl, 3-propoxyphenyl, 4-amyloxyphenyl, 2- hexoxyphenyl, etc., halophenyl, e.g., 2,4,6-trichlorophenyl, 2,4-dibromophenyl, 2-chlorophenyl, etc., hydroxyphenyl, e.g., Z-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, etc., naphthyl, heterocyclic groups suchv as pyridine, alkylpyridine, e.g., 2-alkylpyridine, 3-alkylpyridine, 4-a1kylpyri- 3 dine, etc., in which thealkyl group has from one to six carbon atoms as defined above, alkoxypyridine groups, e.g., 2-alkoxypyridine, 3-alkoxypyridine, 4-alkoxypyridine, etc., hydroxypyridine, e.g., Z-hydroXypyridine, 3-hydroxypyridine, 4-hydroxypyridine, etc., halogen atoms, e.g., chlorine, bromine, etc., sulfonic acid groups, sulfonamido groups, sulfamino groups, sulfamyl groups, sulfanilarnido groups, hydroxy groups, thioalkyl groups in which the alkyl group has from one to six carbon atoms as defined above, carbamyl groups, alkcarbonyl groups in which the alkyl group has from one to six carbon atoms as defined above, alkoxycarbonyl groups in which the alkoxy group has from one to six carbon atoms as defined above, amino groups and substituted amino groups such as NHCOR,

NHR, and --N(R) in which R is an alkyl group having from one to six carbon atoms as defined above.

The 3-indazolinones of our invention are also useful as their salts, e.g., hydrochloride, sulfate, etc.

These B-indazolinone developing agents are illustrated by the following representative developing agents of our invention but the invention is not to be limited to them.

3-indazolinone N-NH iamino 3-indazolinone 5-amlno-3-indazo1inone 6-amino-3-indazolinone 5-am1no-7-phenyl-3-indazolinone chloro-G-amino-3-indazo1lnone (9) NHz NBC 0 CH -acetannidofl-amino-3-indazolinone D INH 5-methyl-3-indazolinone Cl I -NNH

6-ch1oro-3-indazo1inone NNH 5- (2-pyridy1) -3-indazollnone C1130 -N-NH 6-methoxy-3-indazolinone These compounds may be prepared by starting with a compound such as a 2-chlorobenzoic acid which is then reacted with hydrazine followed by removal of Water to efiect ring closure to make the 3-indazolinone. Alternatively, they may be prepared by starting out with 2- carbamylbenzoic acid which is treated with KOBr to produce 2-arninobenzoic acid which is then reacted with nitrous acid, and sulfur dioxide to effect ring closure to give 3-indazolinone. The 3-indazolinones of the above formula in which R R R or R represent atoms or groups other than hydrogen atoms may be prepared using similar reactions in which the particular substituents or substituents which may be readily converted into the desired substituent are present on the benzoic acid starting material used in the synthesis.

The following specific syntheses of representative developing agents will further illustrate the methods used in preparing our developing agents.

Example I Compound 1,3-indazolinone available commercially may be prepared as described by Pfannstiel and'Janecke, Ber. 75 (1942), page 1104.

Example 11 Step 1: Z-amino-fi-nitrobenzoic acid.-This compound was prepared by heating 2-carbamy1-6-nin'obenzoic acid with KO Br according to the procedure described by Kahn, Ber. 35, 3863, page 31.

Step 2: 4-nitro-3-indazolinone.-This compound was prepared by treating 2-amino-6-nitrobenzoic acid with nitrous acid and sulfur dioxide in acid medium according to the process described by Pfannstiel and Ianecke, Ber. 75, 1104 (1942).

Step 3: 4-amino-3-indazolinone dihydrochloride.-This compound was prepared by the reduction of 4-nitro-3- indazolinone hydrochloride with stannous chloride and hydrochloric acid according to the method described in Ber. 75, 1106.

Analysis: C H Cl Calculated for HCl salt 45.3 4.3 19.1 Calculated for di-HCl salt 37.8 4.1 31.9 Found 43.1 4.5 23.8

Example III Step 1: Z-diazo amino-S-nitrobenzoic acid.-This compound was prepared by reacting 2-chloro-5-nitrobenzoic acid with hydrazine according to the process outlined by Pfannstiel and Janecke, Ber. 75, 1101.

Step 2: 5-nitro-3-indazolinone 'l'his compound was prepared from the product of Step 1 according to the method described in Ber. 75, 1101, 1942.

Step 3: 5-amin0-3-indazolin0ne.-This compound was prepared by the reduction of the reaction product of Step 2 according to the above reference.

Example IV 2-Chloro-3-nitrobenzoic acid prepared according to the method of Holleman and De BruynRec. 20, 209 (1901) was reacted according to the Steps 1 through 3 of Example III to produce 7-amino-3-indazolinone.

Example V Developing agent No. 5 is prepared by the method described in Example III starting with the compound. 2- chloro-4-nitrobenzoic acid in place of 2-chloro-S-nitrobenzoic acid.

Example VI Developing agent No. 6 is prepared according to the method described in Example II using 2-carbamyl-4-methyl-6-nitrobenzoic acid in place of 2-carbamyl-6-nitrobenzoic acid in Step 1.

Example VII Developing agent No. 7 is prepared by the synthesis described in Example III but in which 2-chloro-3-phenyl- S-nitro-benzoic acid was used in Step 1 in place of 2- chloro-S-nitrobenzoic acid in Step 1.

Example VIII Developing agent No. 8 is prepared by the procedure described in the synthesis of Example II but in which 2- carbamyl-6-chloro-4-nitrobenzoic acid was used in place of 2-carbamyl-6-nitrobenzoic acid in Step 1.

Example IX Developing agent No. 9 is prepared by the process outlined in Steps 1 and 2 of Example III using 2-chloro- 6-acetamidobenzoic acid, in place of 2-chloro-5-nitrobenzoic acid in Step 1.

' Example X Example XI Developing agent No. 11 is prepared by Steps 1 and 2 of Example II in which 2-carbamyl-4-chlorobenzoic acid was used in place of Z-carbamylbenzoic acid in Step 1.

Example XII Developing agent No. 12 is prepared by Steps 1 and 2 v of the process described in Example III substituting 2- chloro-5-(2-pyridinyl)benzoic acid in place of 2-chloro- 5-nitrobenzoic acid in Step 1.

6 Example XIII Developing agent No. 13 is prepared according to the process described in Steps 1 and 2 of Example III substituting 2-chloro-4-methoxybenzoic acid for 2-chloro-5- nitrobenzoic acid in Step 1.

Although the developing agents of our invention may be incorporated in the developer solutions in the form of their free bases they are usually used in the form of the amine salt such as the hydrochloride, sulfate, etc. These salts may be prepared by methods well known in the art.

The developing agents of our invention ,are used advantageously in alkaline developer solutions for producing images in exposed light-sensitive photographic emulsions'. These solutions which are made alkaline by sodium or potassium hydroxide, sodium sesquicarbonate, sodium carbonate or other suitable alkaline agents, also usually contain from 0 to 200 grams per liter of an alkali sulfite. Developer solutions of this type which are advantageously used for developing silver images in photographic emulsions contain from 10 to 200 grams per liter of'an alkali sulfite. The amino-3-indazolinone developers in developer solutions containing from 0 to 10 grams per liter of the alkali sulfite have the novel property of being able to develop a silver image and then auto-couple to form a dye image. .It should be noted that the auto-coupling reaction occurs only when an amino-3-indazolinone is used as the developing agent in a developer solution containing from 0 to 10 grams per liter of an alkali sulfite. This reaction will not take place if a primary aromatic amino color developer such as p-phenylenediamine, 2-amino-5-diethylaminotoluene hydrochloride, N ethyl B methanesulfonamidoethyl- 3-methyl-4-aminoaniline sulfate, etc., is present in such a developer solution since these developers have a higher development rate than the amino-3-indazolinone and as a result the primary aromatic amino color developer is oxidized in preference to the amino-3-indazolinone so auto-coupling does not occur.

These developers are used to develop images in lightsensitive silver halide emulsions such as the gelatin-silver halide emulsions in which the silver halide is silver chloride, silver bromide, silver iodide, silver chlorobromide, silver: lbrornoiodide etc. The emulsions maybe coated on paper or other opaque support or on any of the well known transparent supports such as cellulose nitrate, cellulose acetate, polyethylene terephthalate, polystyrene, polycarbonates, etc. The emulsions may be sensitized to have speeds that are appropriate for contact printing, projection printing such as are used for photographic print materials or the emulsions may be sensitized to have negative-speed characteristics such as would be characterv ized by photographic film for use in cameras for taking pictures.

The use of developer solutions of our invention to produce silver images is illustrated by the following representative examples but should not be limited to these examples.

Example XIV An exposed strip of photographic paper having a contact-speed silver chloride emulsion was developed in a developer having the following formula:

Grams S-indazolinone 10 Sodium sulfite, desiccated 25 Sodium hydroxide 25 Water to 1 liter.

A good photographic silver image was produced in this sample of paper by 3 minutes of development at 70 F.

Example XV Another exposed sample of photographic paper like that used in Example XIV was developed vigorously and selectively by the following developer solution:

Grams 4-amino-3-indazolinone Sodium sulfite, desiccated 25 7 Sodium sesquicarbonate 75 Water to 1 liter.

As in Example XIV a good silver image was produced by 3 minutes development at 70 F.

Example XVI Similar results were obtained by substituting S-amino- 3-indazolinone in the developer formula of Example XV in place of the 4-amino derivative.

Example XVII Example XVIII A sample of exposed negative-speed photographic film having a fine-grain silver bromoiodide emulsion was developed at 68 F. in the following developer.

Grams 3-indazolinone V 5.6 Sodium sulfite, desiccated 25 Sodium carbonate monohydrate 25 Water to 1 liter.

The pH of the solution was adjusted to 12.8 by the addition of potassium hydroxide. This developer produced a normal degree of development in 7 minutes. Very satisfactory silver images were also produced when other samples of the exposed film were developed with the above formula which contained as low as 2.2 g. of 3-indazolinone per liter of solution.

Another exposed sample of the film was developed in a developer containing hydroquinone as the developing agent at the usual pH of 10. It was found that this developer required 14 minutes to produce the same degree of development produced by the 3-indazolinone developer in 7 minutes.

These developer solutions were compared for stability on aeration. Tests showed that the indazolinone solution did not discolor or show other evidences of deterioration whereas the hydroquinone developer solution became strongly discolored.

Example XIX A developer solution having the formula of the developer of Example XVIII but using 5-amino-3-indazolinone in place of I i-indazolinone and adjusted to a pH of was found to produce a good silver image in an exposed sample of negative-speed photographic film having a fine-grain silver bromoiodide emulsion after 2.5 minutes of development at 68 F.

Similar tests made using p-aminophenol, and hydroquinone as the sole developing agents in place of S-arnino- 3-indazolinone were found to require 4.5 and 13.2 minutes of development respectively, to produce the same amount of development; In another test in which paminophenol and hydroquinone were combined in the same developer solution, it was found that it required 3.2 minutes to produce an image corresponding to that produced by the 5-amino-3 indazolinone developer in 2.5 minutes.

Example XX An exposed sample of photographic film having a negative-speed silver bromoiodide emulsion was developed in a developer solution of Example XVIII containing 5- amino-3-indazoliuone in place of 3-indazolinone for 4 8 minutes at 68 F. giving full emulsion speed, a gross fog of 0.19 and a gamma of 0.77.

The amino-3-indazolinone developing agents of our invention are used as the sole developing agents in alkaline developer solutions containing from 0 to 10 grams per liter of an alkaline sulfite to produce silver and dye images in exposed light-sensitive silver halide emulsion layers. 'I'hese developing solutions are not to be confused with prior art developing solutions used for producing silver and dye images which either contain a color-forming coupler compound in the solution itself or which do not contain the color-forming coupler compound in the solution but are used to develop a photographic film incorporating the color-forming coupler. Our developing solutions produce the silver and dye image without requiring or containing a color-forming coupler compound in either the solution or in the photographic film.

The following examples will illustrate how our developers produce silver and dye. images in photographic emulsion layers.

Example XXI 0.1 gram of 7-amino-3-indazolinone was dissolved in 10 cc. of 3% sodium carbonate solution and 1 drop of this solution was placed on a photographic paper having a projection-speed silver chlorobromide emulsion which had been exposed through a crosshatch grid. A combined silver and magenta image developed in about 15 seconds. The soluble magenta dye leached out into the developer solution. The dye extracted from the developer with ethyl acetate had its maximum absorption at a wavelength of 560 mp.

Example XXII The procedure was repeated with 4-amino-3-indazolinone. This developing agent auto-coupled to form a green dye.

Example XXIII The procedure of Example XXI was repeated with 6- amino-3-indazolinonef A yellow-colored dye was formed in this example by auto-coupling of the developing agent.

Similarly, other amino-3-indazolinone developing agents of our invention may be used in developers to produce dye images in exposed light-sensitive silver halide emulsion layers, in which the dye image is immobilized at the development site or can diffuse to a receiving layer depending upon the solubility characteristics which are determined by the particular developing agent of our invention that is used in this process. The silver image that is produced simultaneously with the dye image is removed by treating the photographic emulsion layer with a bleaching solution such as a potassium ferricyanide bleaching solution well known to the art and followed by treatment in an alkali thiosulfate fiixing bath to leave a dye image.

The developing agents of our invention have been found to act as development accelerators. For example, a developer formula of Example XV but in which ascorbic acid was used in place of 4-amino-3-indazolinone did not develop a sample of exposed photographic paper like that used in Example XV. However, the further addition of as little as 0.5 g. of any of the amino-3-indazolinones caused vigorous development. The S-amino- 3-indazolinones was especially effective in accelerating ascorbic acid development.

The 3-indazolinones of our invention showed superadditive properties when combined in developers with 1- phenyl-S-pyrazolidone or with hydroquinone. Similarly, these super-additive properties may be obtained by combining in developer solutions a 3-indazolinone of our invention with developer soluble hydroquinones that are substituted on the 2,3,5- or 6-carbons or any combination of these with lower alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, etc., with lower alkoxy groups, halogen atoms such as chlorine, bromine, iodine and fluorine and other groups commonly used as substituents, or with 3-pyrazolidones such as 1-phenyl-3- pyrazolidone, l-p-tolyl-3-pyrazolidone, 5-pheny1-3-pyrazolidone and other 3-pyrazolidones such as are listed in Haist et al. US. Patent 2,875,048, issued February 24, 1959, etc.

The B-indazolinone developing agents of our invention are incorporated in dry powder developer compositions of the types described by Kridel et al. US. Patents 2,666,- 702 and 2,666,703, issued January 19, 1954; Wiitala et al. US. Patents 2,682,464 and 2,682,465, issued June 29, 1954; Henn et al. US. Patent 2,685,513, issued August 3, 1954, and Baxendale et al. US. Patent 2,816,026, issued December 10, 1957. 1

Our dry developer compositions contain 3-indazolinone developing agents as the sole developing agent or in combination with other developing agents commonly used for developing exposed silver halide in emulsion layers used for -black-and-white photography, such as p-aminophenol, ascorbic acid, hydnoquinone, substituted hydroquinone as described above, or a 3-pyrazolidone developer such as is described above. Our dry compositions contain an alkali such as sodium carbonate, potassium carbonate, trisodium phosphate, sodium pyroborate, sodium metaborate, sodium hydroxide, potassium hydroxide, etc. Our dry compositions may contain an alkali sulfite such as sodium sulfite, potassium sulfite, etc., an alkali bisulfite such as sodium bisulfite, potassium bisulfiite, etc., an alkali metabisulfite, such as sodium metabisulfite, potassium metalbisulfite, etc. Suificient amounts of these dry materals are used to provide in a solution prepared from the composition, from 0.25 to 30 grams per liter of the 3- indazolinone, from 1 to 100 grams per liter of the alkali and from to 200 grams per liter of the alkali sulfite, alkali bisulfite or alkali metabisulfite.

Other materials may be added to [the dry developer compositions such as the sequestering agents of Henn US. 2,625,476, issued January 13, 1953, and Henn et al. US. 2,656,273, issued October 20, 1953, the stabilizers of Haist et al. US. 2,875,048, issued February 24, 1959, antifoggants commonly used such as benzotriazole, development restrainers such as alkali bromides, etc.

Our 3-indazolinone developing/agents are also incorporated in combined dry developer and fixer compositions. For this purpose an alkali thiosulfate such as sodium thiosulfate, potassium thiosulfate, etc., is incorporated in any of the dry developer compositions containing our 3- indazolinone developing agent described above. Suflicient alkali thiosulfate is used in these compositions to provide from to 200 grams per liter in the solution made from the dry composition.

The novel 3-indazolinone developing agents of our invention can be used advantageously in alkaline developer solutions which are valuable for photographic development. The 3-indazolinone developing agents are used to produce silver images, while the =amino-3-indazolinone developing agents may be used to produce silver, or silver and dye images depending upon the concentration of alkali sulfite that is used in the developer solution. The developing agents used in 1011K developers have very -desirable properties and are found to have higher developer activities than developing solutions containing many of the prior art developing agents. Although the developing agents are usually used as the sole developing agent in the developer solution they may be used together with other developing agents such as ascorbic acid, paminophenol, hydroquinones, and 3-pyrazolidones to produce superadditive eifect-s.

The developer solutions of our invention are further characterized by being considerably more stable than rcor responding developer solutions containing prior art developing agents.

The developer solutions of our invention which are used to produce silver and dye images contain from 0 to 10 grams per liter of an alkali sulfite and use an amino-3- indazolinone developer as the sole developer. In these solutions the amino-3-indazolinones are characterized by their ability to auto-couple and produce dye images without requiring the presence of a color-forming coupler compound in the developer solution or in the light-sensitive emulsion layer. Auto ooupling will not occur from the use of such solutions if a primary aromaticamino developing agent of the color developing type is present in the solution.

The B-indazoline developing agents of our invention are advantageously incorporated as the developing agent in dry powdered photographic developer compositions as well as in combined dry developer and fixer compositions for preparing monobaths.

The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. An alkaline photographic developer composition containing sufiicient alkali sulfite to produce from 0.1 to 200 grams per liter in solution 'and'as the sole developing agent a compound having the formula in which D represents the non-rnetallic atoms necessary to complete a benzene ring.

2. An alkaline photographic developer composition containing suflicient alkali sulfite to produce from 0.1 to 200 grams per liter in solution and as the sole photo graphic developing agent, a compound having the formula:

in which R R R and R are selected from the class consisting of a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an aryl group, a pyridyl group, a halogen atom, an amino group, and a -NHCO'R group in which R is an alkyl group having from 1 to 6 carbon atoms.

3. An alkaline photographic developer composition containing a 3-indazo1inone as the sole developing agent and suflicient alkali sulfite to produce a concentration of from 0.1 to 200 grams per liter in solution.

4. An alkaline photographic developer solution containing as the sole developing agent 7-amino-3-indazolinone, and from 10 to 200 grams per liter of an alkali sulfite.

5. An alkaline photographic developer solution containing as the sole developing agent 4-amino-3-indazolinone, and from 10 to 200 grams per liter of an alkali sulfite.

6. An alkaline photographic developer solution containing as the sole developing agent 6-amino3-inda-.

zolinone, and from 10 to 200 grams per liter of an alkali in which R R R and R are selected from the class consisting of a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, a substituted alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an aryl group, a pyridyl group, a halogen atom, an amino group, and a NI-ICOR group in which R is an alkyl group of from 1 to 6 carbon atoms, such that at least one of the groups R R R and R is an amino group.

9. An alkaline photographic developer solution containing as the sole developing agent 4-chloro-6-am-ino-3- indazolinone and an alkali sulfite at a concentration of from 0.1 to 10 grams per liter.

10. An alkaline photographic developer solution containing as the sole developing agent 7+amino-3-iudazolinone and an alkali sulfite at a concentration of from 0.1 to 10 grams per liter.

11. An alkaline photographic developer solution containing as the sole developing agent 4-amino-3-indazolinone and an alkali sulfite at a concentration of from 0.1 to 10 grams per liter.

12. An alkaline photographic developer solution containing as the sole developing agent 6 an1ino-3-indazolinone and an alkali sulfite at a concentration of from 0.1 to 10 grams per liter.

13. An alkaline photographic developer solution containing as the sole developing agent 5-amino-3-indazolinone and an alkali sulfite at a concentration of from 0.1 to grams per liter.

14. A process for producing an image in an exposed light-sensitive photographic emulsion comprising development with a developer solution of claim 1.

15. An alkaline photographic developer composition containing sufiicient alkali sulfite to produce from 0.1 to 200 grams per liter in solution and as. the sole photographic developing agent a developer selected from the class consisting of 3-indazolinone, 4-arnino-3-indazolinone, 5-amino-3-indazolinon-e, 7-amino-3-indazolinone, G-amino- 3 indazolinone, 4 amino 6 methyl-S-indazolinone, 5- amino-7-phenyl-3indazolinone, 4-chloro-6amino-3-indazolinone, 4-acetamido-7-amino-3indazoiinone, S-methyl- B-indazolinone, 6-chloro-3-indazolinone, 5-(2-pyridy1)-3- indazolinone and 6-methoXy-3-inclazolinone.

16. A process for producing a silver image in an exposed light-sensitive photographic emulsion comprising the steps; development with a developer solution of claim 15, and fixing with an alkali thiosulfate fixing bath.

17. A process for producing a dye image in an exposed light-sensitive photographic emulsion comprising the steps; development with a developer solution of claim 8, bleaching with an alkali ferricyanide bleach solution and fixing with an alkali thiosulfa-te composition.

18. A photographic developer in dry form comprising an alkaline material, an alkali sulfite and as the sole photographic developing agent a compound having the formula:

in which R R R and R are selected from the class consisting of a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an aryl group, a pyridyl group, a halogen atom, an amino group, and a NHCOR group in which R is an alkyl group of from 1 to 6 carbon atoms.

19. A photographic developer in dry form comprising sufficient alkali metal salt to produce 1.0 to grams per liter in solution, a sufficient amount of an alkali sulfite to produce 0.25 to 10 grams per liter in solution, and as the sole photographic developer :a suflicient amount of a compound having the formula:

in which R R R and R are selected from the class consisting of a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an aryl group, a pyridyl group, a halogen atom, an amino group, and a NHCOR group in which R is an alkyl group of from 1 to 6 carbon atoms, such that at least one of the groups R R R and R is an amino group, to produce 0.25 to 30 grams per liter in solution.

20. A photographic developer in dry form comprising suificient alkali metal salt to produce 1.0 to 100 grams per liter in solution, sufiicient alkali sulfite to produce 0.25 to 200 grams per liter in solution, and as the sole photographic developing agcnt a suflicient amount of a compound having the formula:

in which R R R and R are selected from the class consisting of a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an aryl group, a pyridyl group, a halogen atom, an amino group, and a NHCOR group in which R is an :alkyl group of from 1 to 6 carbon atoms, to produce 0.25.to 30 grams per liter in solution.

21. A combined photographic developer and fixer in dry form comprising sufiicient alkali metal salt to produce 1.0 to 100 grams per liter in solution, suflicient alkali metal thiosulfate to produce 5 to 200 grams per liter in solution, suflioient alkali sulfite to produce from 0.25 to 200 grams per liter in solution, and as the sole photographic developing agent a sufficient amount of a compound having the formula:

P fannsteil et'aL: Berichte, 75 (1942), pages 1096-1107. (Copy in Sci. Lib. and Div. 6.) 

8. AN ALKALINE PHOTOGRAPHIC DEVELOPER SOLUTION CONTAINING FROM 0.1 TO 10 GRAMS PER LITER OF AN ALKALI SULFITE AND AS THE SOLE PHOTOGRAPHIC DEVELOPING AGENT A COMPOUND HAVING THE FORMULA:
 17. A PROCESS FOR PRODUCING A DYE IMAGE IN AN EXPOSED LIGHT-SENSITIVE PHOTOGRAPHIC EMULSION COMPRISING THE STEPS; DEVELOPMENT WITH A DEVELOPER SOLUTION OF CLAIM 8, BLEACHING WITH AN ALKALI FERICYANIDE BLEACH SOLUTION AND FIXING WITH AN ALKALI THIOSULFATE COMPOSITION. 